Preparation method of 4, 4 '-dichlorodiphenyl sulfone
Through the azeotropic distillation method of p-chlorobenzenesulfonic acid and chlorobenzene, the existing 4,4’-dichlorodiphenylsulfone production process and environmental pollution are solved, and the preparation of low-cost and high-purity products is achieved.
Patent Information
- Application Number
- CN202411698159.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-25
- Publication Date
- 2025-04-18
AI Technical Summary
The existing 4,4’-dichlorodiphenylsulfone production process is complex, requiring dangerous hydrogen peroxide oxidation or sulfur trioxide processes, and the use of sulfur trioxide requires proprietary equipment, which has safety and environmental problems.
By azeotropic distillation method of p-chlorobenzenesulfonic acid and chlorobenzene, azeotropic distillation and water separation reaction are used, and p-chlorobenzenesulfonic acid is used as an acid catalyst for the reactant and dehydration reaction, so as to avoid the use of aluminum trichloride and waste acid.
It realizes the simple, environmentally friendly and low-cost preparation of high-purity 4,4’-dichlorodiphenylsulfone, avoiding process complexity and safe environmental problems.
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Abstract
Description
Technical Field
[0001] The present application relates to a method for preparing 4,4'-dichlorodiphenyl sulfone. Background Art
[0002] Polyarylethersulfone is divided into polysulfone (PSU or PSF), polyethersulfone (PES or PESU), polyphenylsulfone (PPSU), phenolphthalein type polyarylethersulfone (PES-C), azabiphenyl type polyarylethersulfone (PPES) and polyarylethersulfone (PASF). The molecular structure of polyarylethersulfone gives it excellent properties such as high operating temperature, high strength, good dimensional stability and creep resistance, and it has been widely used in transportation, electronics, medical and mechanical fields.
[0003] Polyarylethersulfone polymers are mainly prepared by aromatic nucleophilic substitution polycondensation reaction. 4,4'-Dichlorodiphenylsulfone ( DCDPS) is more Although DFDPS has a slightly lower reactivity, the raw materials are cheap and easy to obtain, and it is the first choice for the preparation of various polyarylethersulfone materials. At present, the production processes of commercial DCDPS mainly include the dichloride method and the sulfur trioxide method. The dichloride method requires the use of hydrogen peroxide oxidation to obtain the product, and the process itself is a dangerous process, which is bound to lead to increased safety costs. The sulfur trioxide method uses sulfur trioxide to react with chlorobenzene to generate p-chlorobenzenesulfonic acid, which is then reacted with dichloride to generate p-chlorobenzenesulfonyl chloride, and finally reacted with another molecule of chlorobenzene in the presence of aluminum chloride to produce the product. This method has a long route, and the transportation and use of sulfur trioxide require proprietary equipment, which has great limitations. Summary of the invention
[0004] In order to solve the above technical problems existing in the prior art, the present application provides a method for preparing 4,4'-dichlorodiphenyl sulfone. The method provided by the present application does not require the presence of Lewis acid catalysts such as aluminum chloride, and no waste acid is generated, and can obtain high-purity 4,4'-dichlorodiphenyl sulfone products at low cost and in an environmentally friendly manner.
[0005] Specifically, the present application provides a method for preparing 4,4'-dichlorodiphenyl sulfone, which comprises subjecting a mixture of p-chlorobenzenesulfonic acid and chlorobenzene to azeotropic distillation.
[0006] The present application adopts azeotropic distillation water separation reaction of p-chlorobenzenesulfonic acid and chlorobenzene. The former is both a reactant and an acid catalyst for dehydration reaction. No other catalyst or water absorbent needs to be added. The present application can effectively overcome the problems of complex process existing in the existing production process of 4,4'-dichlorodiphenyl sulfone, and obtain high-purity 4,4'-dichlorodiphenyl sulfone products in a simple, environmentally friendly and low-cost manner.
[0007] In some embodiments, the preparation method comprises the following steps:
[0008] S1: subjecting a mixture of p-chlorobenzenesulfonic acid and chlorobenzene to azeotropic distillation to obtain a gas phase component;
[0009] S2: The liquid phase components after the gas phase components are condensed enter the water separation device;
[0010] S3: After the liquid components in the water separation device are dehydrated, they are circulated to step S1 for azeotropic distillation;
[0011] S4: Repeat steps S2-S3 at least once to obtain a reaction solution.
[0012] In some embodiments, chlorobenzene and water produce an azeotrope during the azeotropic distillation.
[0013] In some embodiments, in step S1, the gas phase components include chlorobenzene and water.
[0014] In some embodiments, in step S1, the temperature of the azeotropic distillation is 130°C-150°C, for example, 131°C, 133°C, 135°C, 137°C, 139°C, 140°C, 141°C, 143°C, 145°C, 147°C, 149°C or any value therebetween. In some embodiments, the temperature of the azeotropic distillation is 135°C-145°C.
[0015] In some embodiments, in step S1, the mass ratio of p-chlorobenzenesulfonic acid to chlorobenzene is 1:(2-10), such as 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or therebetween. In some embodiments, the mass ratio of p-chlorobenzenesulfonic acid to chlorobenzene is 1:(3-7).
[0016] In some embodiments, in step S2, when the volume of the liquid phase component is 3 / 4-1 of the volume of the water separation device, the liquid phase component is dehydrated.
[0017] In some embodiments, dehydration is performed using anhydrous magnesium sulfate.
[0018] In some embodiments, in step S4, steps S2-S3 are repeated at least five times, for example 5 times, 10 times, 15 times, 20 times, 25 times, 30 times, 35 times, 40 times, 45 times, 50 times, 55 times, 60 times, 65 times, 70 times, 75 times, 80 times, 85 times, 90 times, 95 times, 100 times, 110 times, 120 times, 130 times, 140 times, 150 times, 160 times, 170 times, 180 times, 190 times, 200 times, 250 times, 300 times or any value therebetween. In some embodiments, steps S2-S3 are repeated five to 150 times.
[0019] In some embodiments, the preparation method further comprises step S5: washing the reaction solution in step S4 with water to obtain an organic phase and an aqueous phase, and drying the organic phase to obtain the 4,4'-dichlorodiphenyl sulfone.
[0020] In some embodiments, the drying process includes spin drying and vacuum drying.
[0021] The beneficial effects of this application are:
[0022] (1) DCDPS was prepared by azeotropic distillation for the first time;
[0023] (2) Chlorobenzene is dried over magnesium sulfate and then added back into the reaction system to continue to carry water, effectively saving costs;
[0024] (3) No aluminum chloride is required as a catalyst;
[0025] (4) No waste acid is produced. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 The synthesis steps of DCDPS according to some embodiments of the present application are shown.
[0027] Figure 2 Schematic diagram of the reaction apparatus used in the preparation of DCDPS in some embodiments of the present application. DETAILED DESCRIPTION
[0028] In order to make the purpose, technical solution and advantages of the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. The specific embodiments described here are only used to explain the present application and are not intended to constitute any limitation to the present application.
[0029] The present application provides a method for preparing 4,4'-dichlorodiphenyl sulfone, specifically, as follows Figure 1 As shown, p-chlorobenzenesulfonic acid and chlorobenzene undergo azeotropic distillation to separate water, and p-chlorobenzenesulfonic acid is both a reactant and an acid catalyst for the dehydration reaction. The method provided by the present application does not require the addition of other catalysts or water absorbents, does not generate waste acid, and can obtain a high-purity 4,4'-dichlorodiphenyl sulfone product at a low cost and in an environmentally friendly manner.
[0030] In some embodiments, the preparation method of 4,4'-dichlorodiphenyl sulfone provided in the present application comprises the following specific steps:
[0031] Use Figure 2In the reaction device shown, chlorobenzene and p-chlorobenzenesulfonic acid are added to a four-necked reaction bottle, electromagnetic stirring is turned on, and heating is turned on. After the temperature reaches the reflux temperature, for example, 130°C-140°C, reflux begins, and the liquid distilled from the water separator is first clear and then becomes turbid. As the reaction proceeds, the upper layer becomes clear and the lower layer becomes turbid. When the liquid in the water separator is full, the liquid is released, dried over anhydrous magnesium sulfate, and then added back to the four-necked reaction bottle to continue azeotropic distillation.
[0032] Repeat the above water separation operation for at least 5 times to obtain a reaction solution. After the reaction solution is cooled, it is washed with water to separate the organic phase and the aqueous phase. The organic phase is respectively spin-dried and vacuum-dried to obtain the dichlorodiphenyl sulfone product.
[0033] The present application is further described below through specific examples.
[0034] Example 1
[0035] Add 56.28 grams of chlorobenzene and 19.26 grams of p-chlorobenzenesulfonic acid into a four-necked bottle, turn on magnetic stirring, and turn on heating. When the temperature reaches 139°C, reflux begins. The liquid distilled from the water separator is clear at first and then becomes turbid. As the reaction proceeds, the upper layer becomes clear and the lower layer becomes turbid. When the liquid in the water separator is full, release the liquid, dry it over anhydrous magnesium sulfate, and add it back to the four-necked bottle to continue azeotropic distillation. Repeat the water separation operation 5 times, 50 mL each time, and the total amount of chlorobenzene repeated reflux is 250 mL.
[0036] After the reaction solution was cooled, water was added for washing, and the organic phase and the aqueous phase were separated. The organic phase was respectively spin-dried and vacuum-dried to obtain 7.50 g of dichlorodiphenyl sulfone DCDPS, with a yield of 26.1% and a gas chromatography purity of 99.37%.
[0037] Example 2
[0038] Add 56.28 grams of chlorobenzene and 19.26 grams of p-chlorobenzenesulfonic acid into a four-necked bottle, turn on magnetic stirring, and turn on heating. When the temperature reaches 139°C, reflux begins. The liquid distilled from the water separator is clear at first and then becomes turbid. As the reaction proceeds, the upper layer becomes clear and the lower layer becomes turbid. When the liquid in the water separator is full, release the liquid, dry it over anhydrous magnesium sulfate, and add it back to the four-necked bottle to continue azeotropic distillation. Repeat the water separation operation 15 times, 50 mL each time, and the total amount of chlorobenzene repeated reflux is 750 mL.
[0039] After the reaction solution was cooled, water was added for washing, and the organic phase and the aqueous phase were separated. The organic phase was respectively spin-dried and vacuum-dried to obtain 15.29 g of dichlorodiphenyl sulfone DCDPS, with a yield of 53.2% and a gas chromatography purity of 99.49%.
[0040] Example 3
[0041] Add 56.28 grams of chlorobenzene and 19.26 grams of p-chlorobenzenesulfonic acid into a four-necked bottle, turn on magnetic stirring, and turn on heating. When the temperature reaches 139°C, reflux begins. The liquid distilled from the water separator is clear at first and then becomes turbid. As the reaction proceeds, the upper layer becomes clear and the lower layer becomes turbid. When the liquid in the water separator is full, release the liquid, dry it over anhydrous magnesium sulfate, and add it back to the four-necked bottle to continue azeotropic distillation. Repeat the water separation operation 25 times, 50 mL each time, and the total amount of chlorobenzene repeated reflux is 1250 mL.
[0042] After the reaction solution was cooled, water was added for washing, and the organic phase and the aqueous phase were separated. The organic phase was respectively spin-dried and vacuum-dried to obtain 19.40 g of dichlorodiphenyl sulfone DCDPS, with a yield of 67.5% and a gas chromatography purity of 99.16%.
[0043] Example 4
[0044] Add 56.28 grams of chlorobenzene and 19.26 grams of p-chlorobenzenesulfonic acid into a four-necked bottle, turn on magnetic stirring, and turn on heating. When the temperature reaches 139°C, reflux begins. The liquid distilled from the water separator is clear at first and then becomes turbid. As the reaction proceeds, the upper layer becomes clear and the lower layer becomes turbid. When the liquid in the water separator is full, release the liquid, dry it over anhydrous magnesium sulfate, and add it back to the four-necked bottle for continuous azeotropic distillation. Repeat the water separation operation 50 times, 50 mL each time, and the total amount of chlorobenzene repeated reflux is 2500 mL.
[0045] After the reaction solution was cooled, water was added for washing, and the organic phase and the aqueous phase were separated. The organic phase was respectively spin-dried and vacuum-dried to obtain 24.01 g of dichlorodiphenyl sulfone DCDPS, with a yield of 83.6% and a gas chromatography purity of 99.23%.
[0046] Example 5
[0047] Add 56.28 grams of chlorobenzene and 19.26 grams of p-chlorobenzenesulfonic acid into a four-necked bottle, turn on the magnetic stirring, and turn on the heating. When the temperature reaches 139°C, reflux begins. The liquid distilled from the water separator is clear at first and then becomes turbid. As the reaction proceeds, the upper layer becomes clear and the lower layer becomes turbid. When the liquid in the water separator is full, release the liquid, dry it over anhydrous magnesium sulfate, and add it back to the four-necked bottle for continuous azeotropic distillation. Repeat the water separation operation 100 times, 50 mL each time, and the total amount of chlorobenzene repeated reflux is 5000 mL.
[0048] After the reaction solution was cooled, water was added for washing, and the organic phase and the aqueous phase were separated. The organic phase was respectively spin-dried and vacuum-dried to obtain 26.91 g of dichlorodiphenyl sulfone DCDPS, with a yield of 93.7% and a gas chromatography purity of 99.65%.
[0049] The technical solution of the present application is not limited to the above-mentioned specific embodiments, and all technical variations made according to the technical solution of the present application fall within the protection scope of the present application.
Claims
1. A method for preparing 4,4'-dichlorodiphenyl sulfone, comprising subjecting a mixture of p-chlorobenzenesulfonic acid and chlorobenzene to azeotropic distillation.
2. The preparation method according to claim 1, characterized in that: The preparation method comprises the following steps: S1: subjecting a mixture of p-chlorobenzenesulfonic acid and chlorobenzene to azeotropic distillation to obtain a gas phase component; S2: The liquid phase components after the gas phase components are condensed enter the water separation device; S3: After the liquid components in the water separation device are dehydrated, they are circulated to step S1 for azeotropic distillation; S4: Repeat steps S2-S3 at least once to obtain a reaction solution.
3. The preparation method according to claim 1 or 2, characterized in that: In step S1, the gas phase components include chlorobenzene and water.
4. The preparation method according to claim 1 or 2, characterized in that: In step S1, the temperature of the azeotropic distillation is 130°C-150°C; and / or In step S1, the mass ratio of p-chlorobenzenesulfonic acid to chlorobenzene is 1:(2-10).
5. The preparation method according to claim 1 or 2, characterized in that: In step S1, the temperature of the azeotropic distillation is 135°C-145°C; and / or In step S1, the mass ratio of p-chlorobenzenesulfonic acid to chlorobenzene is 1:(3-7).
6. The preparation method according to claim 1 or 2, characterized in that: In step S2, when the volume of the liquid phase component is 3 / 4-1 of the volume of the water separation device, the liquid phase component is dehydrated.
7. The preparation method according to claim 1 or 2, characterized in that: In step S3, anhydrous magnesium sulfate is used for dehydration; and / or In step S4, steps S2-S3 are repeated at least five times.
8. The preparation method according to claim 1 or 2, characterized in that: In step S4, steps S2-S3 are repeated five to 150 times.
9. The preparation method according to claim 1 or 2, characterized in that: The preparation method further comprises step S5: washing the reaction solution in step S4 with water to obtain an organic phase and an aqueous phase, and drying the organic phase to obtain the 4,4'-dichlorodiphenyl sulfone.
10. The preparation method according to claim 9, characterized in that: The drying process includes spin drying and vacuum drying.